Interdigitated finger coextrusion

ABSTRACT

A co-extrusion device has at least one first inlet port to receive a first material, at least one second inlet port to receive a second material, a first combining channel arranged to receive the first material and the second material and combine the first and second materials into a first combined flow flowing in a first direction. a splitter channel arranged to receive the first combined flow and to split the first combined flow into at least two split flows in a second direction at least partially orthogonal to the first direction, wherein each split flow consists of the first and second materials, and a second combining channel arranged to receive the split flows and combine the split flows into a second combined flow in the first direction, and at least one exit orifice arranged to allow the materials to exit the device as a single flow. A method for depositing a structure comprising interdigitated materials includes merging flows of at least two materials in a first direction into a first combined flow, dividing the first combined flow in a second direction to produce at least two separate flows, wherein the second direction is perpendicular to the first direction, and merging the two separate flows into a second combined flow.

BACKGROUND

Numerous devices such as batteries, fuel cells, electrical interconnectsand others can benefit from tightly spaced interdigitated stripes ofdissimilar materials. The term ‘stripe’ as used here means a line orother shape of material that contains only that material. It does notmix with adjacent stripes of other materials.

Issues arise when trying to produce tightly spaced interdigitatedstripes. In one approach, flow focusing compression produces finefeatures of functional material in paste form. Examples of this approachcan be found in U.S. Pat. Nos. 7,765,949, issued Aug. 3, 2010; and7,799,371, issued Sep. 21, 2010. The approach taken in these patentsrelates to combining materials into ‘co-laminar’ flows, where threelaminar flows of two different materials are brought together to formone flow, but where the two materials do not mix together. This approachsuffices in application where the features are on the order of tens ofmicrons arrayed on a millimeter scale pitch. For example, a solar cellmay have a width of 156 mm and about 80 gridlines, each about 50 micronswide separated by almost 2 mm from a neighboring gridline.

In contrast, the interdigitated structures called for in the design ofelectrodes for energy storage devices may require micron scale featuresinterleaved on the micron scale. For example, a typical cathodestructure may involve interleaved structures that are 5 microns wide and100 microns tall. An electrode structure may be 300 mm wide and 60,000interleaved fingers of dissimilar materials. To dispense these materialsfrom separate nozzles or in from multi-material slot containers would beimpractical.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a block diagram of a fluid flow of two materials into aninterdigitated single flow.

FIG. 2 shows an isometric view of an embodiment of a fluid path.

FIG. 3 shows exploded view of an embodiment of a fluid co-extrusiondevice.

FIG. 4 shows an embodiment of a co-extrusion device and a substrate.

FIG. 5 shows an embodiment of a metal air battery having interdigitatedstructures.

FIGS. 6-10 show embodiments of interdigitated co-extrusions.

DETAILED DESCRIPTION OF THE EMBODIMENTS

In order to attain an interdigitated structure having micron features ona micron scale, it is possible to combine and focus two or more flows,split the combined flow into separate combined flows and then recombineand further focus the flows in repeated stages. This discussion willrefer to the fluidic process that produces interdigitated flows ofdissimilar fluids as ‘fluid folding.’ This discussion may also refer tothe fluidic structure that performs the operations of combining,focusing, splitting, and recombining, etc., as a ‘folding cascade.’

The term ‘focusing’ as used here means the combining of two or moreflows of dissimilar fluids into a combined flow that has a lateralextent across the width of the combined flow at least less than thecombined lateral extent of the flows prior to combination. Typically thewidth of the combined flow after focusing has a lateral extent thatapproximately equals the lateral extent across one of the flows prior tocombination. For example, if a combined flow consists of one ‘stripe’ orfinger each of material A and material B, the combined flow will have alateral extent of measure X. When the flow is split and then recombined,now having two stripes each of materials A and B interleaved, thelateral extent of this flow will have the same lateral extent X of theprevious flow.

FIG. 1 shows a cross sectional diagram of a flow of two materials. Allflows in FIG. 1 are in the direction of the axis that runs perpendicularto the page. All flows are shown in cross section coming out of thepage. Material A, 10, and material B, 12, flow separately from eachother at stage 14. They then combined at stage 16 to form a firstcombined flow. This flow is focused at stage 18. It should be noted thatthe combining and focusing may occur simultaneously or stepwise withinthe cascade.

At stage 20, the combined flow splits into two separate combined flows.Note that the cascade is three dimensional, so the splitting occurs in adirection orthogonal to both the flow direction and the initialcombining and focusing, that is, up and down in the figure.

The two combined flows move separately from each other and are directedto be in lateral proximity at stage 22. At stage 24, the two separatecombined flows are combined into a second combined flow, which is thenfocused at stage 26. This combined flow is then split again at stage 28in a similar or identical fashion as at stage 20, separated at stage 30and then recombined at stage 32. At 34, the combined flow is thenfocused. While this process may repeat as many times as desired, onlylimited by the ability of the materials to remain separated from eachother with no complete mixing when combined, at some point the combinedflow will exit the cascade as a single flow through an exit orifice ornozzle. An advantage of this technique lies in its ability to producematerial features much smaller and more numerous than the fluidicchannels that convey them.

FIG. 2 shows an embodiment of a cascade. A first material enters thecascade through channel 40, and a second material enters the cascadethrough a channel 42. Note that these channels, referred to asseparating channels as they separate or maintain the separation betweenflows, may curve to one side or the other and change levels. The twoflows are combined using a combining channel 44. As discussed above, thecombining channel has a focusing region 46 in which the combined flow iscompressed or focused into a channel having a lateral extentapproximately equal to the lateral extent of either of the individualseparating channels 40 and 42.

The combined flow is then split into two separate combined flows at thejunction of the combining channel 46 and the splitter channels 50 and48. As shown in FIG. 2, the splitter channels split the flows in adirection orthogonal to the direction of the combined flow in thecombining channel 46. In this example, the combined flow is split ‘up’and ‘down’ relative to the combining channel 46. The direction may notbe fully orthogonal, but may be partially orthogonal, such as goingupwards at an angle between straight up and straight ahead. Eachcombined flow in the splitting channels 50 and 48 consists of a stripeor finger of the first material and a stripe or finger of the secondmaterial. As mentioned above, the device is three dimensional and may beformed from layers.

The two separated combined flows are recombined into a second combinedflow by combining channel 52, which also focuses the second combinedflow. The second combined flow in this example consists of fourinterleaved fingers, two each of the first and second materials. Asecond set of splitter channels, 58 and 54 then split the secondcombined flow into two separate combined flows. The structure 58includes another combining channel, forming a third combined flow of 8interleaved fingers, 4 each of the first and second materials.Optionally the structure 58 may also include an exit orifice withchamfered walls to allow the combined flow to exit the cascade as asingle flow.

In operation, looking at FIG. 2, a first material enters the cascade atlayer +1 at 40. The combining layer acts as the reference layer 0. Asecond material then enters the cascade at layer −1 42. These twomaterials combine into combined flow at layer 0, in this case at Ystructure 46. Note that the combined flow consists of two stripes ofmaterial, one each of the first and second materials. Splitter channels48 and 50 then separate the combined flow into two separate combinedflows, each flowing into layers +1 and −1. The layers then recombineinto a second combined flow at 52. Note that the combined flow now has 4stripes of material, 2 each of the first and second materials.

One should note that the structure of FIG. 2 may have abrupt transitionsbetween the layers. This may result in dead volumes in the corners ofthe various transitions where the materials congregate in the cornersinitially and the remaining flow passes by the congregated material.However, over time, and with the device starting and stopping, thecongregated material may harden or otherwise clog the exit orifices. Inaddition these abrupt transitions may induce flow irregularities whichcan lead to substantial or complete mixing of the materials in thestripes. It may then be desirable to have the flow ‘swept,’ meaning thatthe corners are angled or other wise machined, cut or formed, toeliminate the abrupt steps. This is discussed in co-pending application“Oblique Angle Micromachining of Fluidic Structures,” (Attorney DocketNo. 20100587-US-NP-9841-0215).

The splitting and combining processes may continue as long as desiredwithin the constraints of the fluids, which may be pastes, to maintaintheir individual compositions without complete mixing. At each stage ofcombining and focusing, the line count doubles and the width isdecreased for each line by a factor of 2. The cumulative line widthreduction is 2^(n), which is the same for the number of lines. From amanufacturing standpoint, it is useful for the device to be assembledfrom layers fabricated separately and then stacked with an alignmenttolerance. The layers are then clamped or bonded together. FIG. 3 showsan embodiment of such a device.

In this embodiment, the device consists of 9 layers. In this particularexample, bolts, such as that would use bolt hole 63, clamp the devicetogether through corresponding holes on all of the layers. The twomaterials enter from opposite sides of the device. However, this is justan example and no limitation to any particular configuration isintended, nor should any be implied. Further, this particular exampleuses two materials and has 3 cascades repeated 25 times. These allconsist of examples to aid in the understanding of the invention and nolimitation to any particular configuration is intended nor should it beimplied.

A first material enters the device through the sealing plate 63 andenters distribution manifold 61 and the second material enters throughthe opposite facing sealing plate 59 and enters distribution manifold65. Each manifold produces a substantially equalized source of fluidpressure to an array of cascades that will perform the fluid folding.

Optional layers 71 and 75 contain series of ports 60 and 70,respectively. These layers provide one entry point for each of thecascades in the device, and may contribute to the equalization of thepressures of the materials entering the cascades. These layers may alsobe referred to as layers −2 and +2, in order to correspond to the layerreference used above.

On a first fluid folding layer 71, the array of ports 70 conveys a firstfluid from its distribution manifold to an array of separation channels62 on a second fluid folding layer 81. The first fluid is divertedlaterally in a first direction on the second fluid folding layer. On athird fluid folding layer 75, an array of ports 70 conveys a secondfluid from its distribution manifold to an array of separation channels72 on a fourth fluid folding layer 85. On the fourth fluid folding layer85, the second fluid is diverted laterally in a second directionopposite the first direction.

The directions of the separation channels may be flexible. Forconvenience, in this embodiment all of the separation channels on agiven layer all curve in the same direction. Looking at layer 81, forexample, the separation channels in arrays 62, 64 and 66 all divert theflows laterally towards the right side of the drawing. These channelscould go in different directions, or could all go to the left as well.The same holds true for the separating channels on layer 85 in arrays72, 74 and 76.

On a fifth fluid folding layer 95, flows from the second and fourthlayers are combined and focused into a co-laminar flow by the combiningchannels in array 80. The flows then split ‘vertically’ into two flowson the second and fourth folding layers through arrays 64 and 74,respectively. A first combined flow is diverted laterally in the firstdirection on the second fluid folding layer using array 64. The secondcombined flow is diverted laterally into an array of separation channelson the fourth fluid folding layer using array 74.

The flows then return to the fifth fluid folding layer 95, where theycombine and focus into a second combined, co-laminar flow using array82. This process repeats n times, each time doubling the number ofinterdigitated stripes of materials. Downstream of the final stage ofthe splitting and separating, the flows from all of the cascades areoptionally combined together to a common extrusion slot orifice. In theexample provided, there are 3 repetitions of the process resulting in 8interdigitated stripes from each cascade. There are 25 cascades, so theresulting flow will have 200 interdigitated stripes, 100 of eachmaterial.

One should note that while the device shown here has the materialsarranged on opposite sides of the extruding orifice, the materials couldbe introduced on the same side of the orifice

This co-extrusion device of FIG. 3 can be configured and moved relativeto a substrate to deliver the lines of material, as shown in FIG. 4 asdevice 104. The substrate 102 would be positioned in close proximity tothe applicator at a distance that is on the order of 10-1000 microns,referred to as the working distance. The substrate moves relative to thedevice at a speed comparable to the speed with which fluid exits fromthe printhead/applicator 106. The co-extrusion device contains the fluidreservoirs as well as the printhead/applicator 106, as well as controland power circuitry. Optionally the fluid reservoirs may be locatedremotely and fluids delivered to the device as needed through hoses orother plumbing.

In one embodiment, the printhead assembly is configured with componentsthat are chamfered or cut away in such a manner, typically at 45degrees, that the layered assembly may be held a close proximity to thesubstrate at a tilted angle. The tilt of the printhead assembly enablesa feature that the paste exiting the fluid exit orifice forms an obtuseangle (between 90 and 180 degrees) with the deposited paste on thesubstrate. This reduces the bending strain on the extruded paste whichcan aid in the preservation of interdigitated feature fidelity, reducemixing, and increase print speed.

A co-extrusion device such as that shown in FIGS. 2-4 may be used toform devices that benefit from tightly spaced interdigitated stripes ofdissimilar materials including batteries, fuel cells, electricalinterconnects and others. In the case of interconnects, verticallystacked integrated circuits may be interconnected along their edges witha series of metal lines separated by insulating spacers. In the case ofelectrochemical devices such as fuel cells and batteries, theinterdigitated structures can enhance performance in a variety of ways.Air cathodes of metal air batteries could be structured to haveinterdigitated regions of hydrophilic and hydrophobic regions. This willtypically exhibit improved oxygen reduction activity, improving thepower output of the device.

FIG. 5 shows an example of such a device 110. A hydrophobic membrane 114has an electrode 112 residing on it. A separator 116 resides on theelectrode 112. The electrode in this example consists of interleavedfingers of porous, hydrophobic regions 118 and porous hydrophilicelectro-catalyst regions 120. As mentioned above, this can exhibitimproved oxygen reduction activity and improve power output. Further,increasing the surface area of the three-phase boundary where the solidcatalyst particle, liquid electrolyte and gas-phase reactant interact.For expensive catalysts such as platinum, such structures offer thepotential of significant cost reduction.

FIGS. 6-10 show embodiments of interdigitated co-extrusion structuresparticularly useful to battery electrode formation. In FIG. 6, theelectrode 130 consists of two materials. A first material 132 is anelectrode material, such as a cathode or anode active electrode. Thematerial 134 is ionically conductive material, either through solidelectrolyte conduction or through porosity. Alternatively, the regionsof material 134 may be fugitive or sacrificial material removed during alater drying or firing stage in the manufacturing process. In FIG. 6,the thinner, ionically conductive regions traverse the entire thicknessof the electrode layer.

In one embodiment of the formation process for such a feature, theinitial flows prior to folding may consist of two flows of material, oneof 134 and one of 132. Alternatively, there could be three flows priorto folding, one of material 134 surrounded by flows of 132. This can beimportant if the two materials interact differently with the walls ofthe fluidic channels which otherwise could cause lack of symmetry in thecombining, mixing and separation of the flows.

One should note that the deposition of the electrically conductivecathode or anode material and the second material onto the membraneresult in a structure having interdigitated features of differentmaterials in fluid form. Fluid, as that term is used here, means a gel,a paste, a slurry or a suspension. While these structures may progressthrough drying or firing stages, they will initially exist in a fluidform.

Further, at least one of these structures will generally have a highaspect ratio. As used here, the aspect ratio means the ratio of themaximum height to the maximum width of a structure or feature. Lookingat FIG. 6, one can see that the feature 134 in the interdigitatedstructure has a high aspect ratio, its height, running in the directionfrom the top of the page to the bottom, is much larger than its width,running from the left to right across the page. Generally, at least oneof the features formed from one of the interdigitated materials willhave an aspect ratio greater than 1.

In an alternative embodiment, shown in FIG. 7, the ionically conductingregion does not traverse the full thickness of the electrode. This canbe formed in two processes, first forming a blanket coat of cathode oranode material followed by an interdigitated coat of the ionicallyconducting region and the electrode material. A single-step approachwould make use of poly-extrusion where the blanket electrode materialwould be introduced under the ionically conducting material by tailoringthe timing of the introduction of the materials into the printhead.

One must note that the proportions of the materials differ greatly, withthe cathode or anode material 132 having a much greater width than theionically conductive material 134. This may occur in many differentways. For example, the input channels, such as 42 and 40 from FIG. 2,may have different sizes. Alternatively, the flow rate of material putinto the channels could differ, with much more of the material 132entering one of the channels than the material 134.

In FIG. 8, a third material is introduced through the printhead, in thiscase a principally electrically conducting material 140, where the term‘principally’ refers to the material having a higher expression of therelevant characteristic than the other materials. The manipulation ofmaterials in the printhead and the subsequent folding processes can becontrolled to allow these types of structures to be formed. For example,the three materials can be combined in a three way folding operation toform the central layer of the structure and two layer folding can beperformed prior to and subsequent to the application of the centrallayer. This can be performed with three sequential applicators orunified in a single applicator which executes all three foldingoperations. In this embodiment it will be important to align the fluidiclayers so that the features in FIG. 9 are continuous through theextruded structure.

FIG. 9 shows a structure similar to that of FIG. 7, where the material134 was a fugitive material, removed after printing leaving a gap suchas 142. FIG. 10 shows an embodiment similar to FIG. 8, with the fugitivematerial removed leaving gaps 142, and having the principallyelectrically conducting material 140. These gaps could be subsequentlyfilled with electrolyte material such as a liquid electrolyte to makesubstantially ionically conducting regions within the electrodestructure.

These gaps could also subsequently be filled with the opposite of thecathode or anode material and a spacer material which preventselectrical contact of the anode and cathode materials but allows ionictransport between the electrodes, forming the opposing electrodes of anelectrochemical cell such as a battery with alternating cathode andanode regions. Alternatively these gaps could be filled with a secondelectrode material and spacer material forming the opposing electrodesof an electrolytic capacitor or supercapacitor.

One alternative mentioned previously in the discussion involved flowingthree materials. Referring back to FIG. 2, one can see a possibility ofaltering the initial flow. Instead of having only two input channels 40and 42 in to the combining channel 46, one could have three or moreinput channels. An example of this is shown by combination channel 146in FIG. 11. In FIG. 11, the combination channel has 3 input channels,allowing combination of 3 materials. From this point forward in theprocess, the remaining structure would be the same. Instead of foldingtwo-material flows, however, the remaining structures would foldthree-material flows. More than 3 input channels could also be used;this merely provides an example of more than 2 materials.

In this manner, interdigitated structures having micron features on amicron scale can be formed using a co-extrusion device. The co-extrusiondevice may take the form of a printhead, allowing faster formation ofthe structures using printing techniques.

It will be appreciated that several of the above-disclosed and otherfeatures and functions, or alternatives thereof, may be desirablycombined into many other different systems or applications. Also thatvarious presently unforeseen or unanticipated alternatives,modifications, variations, or improvements therein may be subsequentlymade by those skilled in the art which are also intended to beencompassed by the following claims

1. A co-extrusion device, comprising: at least one first inlet port toreceive a first material; at least one second inlet port to receive asecond material; a first combining channel arranged to receive the firstmaterial and the second material and combine the first and secondmaterials into a first combined flow flowing in a first direction; asplitter channel arranged to receive the first combined flow and tosplit the first combined flow into at least two split flows in a seconddirection at least partially orthogonal to the first direction, whereineach split flow consists of the first and second materials; a secondcombining channel arranged to receive the split flows and combine thesplit flows into a second combined flow in the first direction; and atleast one exit orifice arranged to allow the materials to exit thedevice as a single flow.
 2. The co-extrusion device of claim 1, thecombining channels further arranged to focus the combined flows suchthat the combined flows have a lateral extent less than the lateralextent of sum of the lateral extents of the individual flows previous tothe flows being combined.
 3. The co-extrusion device of claim 1, theco-extrusion device having multiple splitter channels and combiningchannels.
 4. The co-extrusion device of claim 3, wherein the exitorifice is in fluidic communication with a final combining channel toallow the materials to exit the device as a final combined flow.
 5. Theco-extrusion device of claim 1, wherein the channels in the device areswept.
 6. The co-extrusion device of claim 1, wherein the exit orificeis chamfered.
 7. The co-extrusion device of claim 6, wherein the deviceresides adjacent a substrate at an angle relative to the substrate. 8.The co-extrusion device of claim 1, further comprising a third inletport to receive a third material, the first combining channel arrangedto receive the first, second and third materials and combine them intothe first combined flow.
 9. A co-extrusion device, comprising: a firstsheet of material having at least one array of separating structures andat least one array of splitting structures, the separating structuresand the splitting structures having entrances and exits; a second sheetof material arranged adjacent the first sheet of material, the secondsheet of material having at least one array of combining structures andat least one array of extruding structures, the combining structureshaving entrances and exits; the exits of the separating structures beingaligned with the entrances of the combining structures; the exits of thecombining structures being aligned with the entrances of the splittingstructures; and the exits of the splitting structures being aligned withthe entrances of one of either another array of combining structures oran array of extruding structures.
 10. The co-extrusion device of claim9, further comprising a third sheet of material, arranged adjacent aside of the second sheet of material opposite the first sheet ofmaterial.
 11. The co-extrusion device of claim 10, wherein the firstsheet of material is arranged to receive a first material.
 12. Theco-extrusion device of claim 11, wherein the third sheet of material isarranged to receive a second material.
 13. The co-extrusion device ofclaim 12, further comprising a first distribution manifold arrangedadjacent the first sheet of material and a second distribution manifoldis arranged adjacent the third sheet of material, each distributionmanifold arranged to deliver a different material from the otherdistribution manifold.
 14. The co-extrusion device of claim 9, furthercomprising a print head.
 15. The co-extrusion device of claim 9, whereinthe first sheet of material comprises one array of separating structuresand two arrays of splitting structures.
 16. The co-extrusion device ofclaim 9, wherein the second sheet of material comprises two arrays ofcombining structures and one array of extruding structures.
 17. Theco-extrusion device of claim 9, wherein the combining structures furthercomprising combining and focusing structures having a lateral extent ina combining region approximately the same as a lateral extent of aregion prior to the combining region.
 18. A method for depositing astructure comprising interdigitated materials, comprising: merging flowsof at least two materials in a first direction into a first combinedflow; dividing the first combined flow in a second direction to produceat least two separate flows, wherein the second direction isperpendicular to the first direction; merging the two separate flowsinto a second combined flow.
 19. The method of claim 18, wherein themerging flows of at least two materials comprises merging the flows intoa combined flow having a lateral extent less than the lateral extent ofsum of the lateral extents of the individual flows previous to the flowsbeing combined.
 20. The method of claim 18, further comprisingdepositing the second combined flow onto a substrate.
 21. The method ofclaim 18, wherein the dividing and merging are repeated as needed toattain a final combined flow having a predetermined number ofinterdigitated regions.
 22. The method of claim 18, wherein the flow ofa first material has a larger amount or material than the flow of asecond material.
 23. The method of claim 18, wherein merging flows of atleast two materials comprising merging flows of three or more materials.